119 resultados para ULLMANN
Resumo:
The prospect of synthesizing ordered, covalently bonded structures directly on a surface has recently attracted considerable attention due to its fundamental interest and for potential applications in electronics and photonics. This prospective article focuses on efforts to synthesize and characterize epitaxial one- and two-dimensional (1D and 2D, respectively) polymeric networks on single crystal surfaces. Recent studies, mostly performed using scanning tunneling microscopy (STM), demonstrate the ability to induce polymerization based on Ullmann coupling, thermal dehalogenation and dehydration reactions. The 2D polymer networks synthesized to date have exhibited structural limitations and have been shown to form only small domains on the surface. We discuss different approaches to control 1D and 2D polymerization, with particular emphasis on the surface phenomena that are critical to the formation of larger ordered domains.
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Liederkranzausflug nach Hundseck; Standing l-r; Sidi Ullmann, Ehepaar, Alfred und Toni Hirschland, Willi Ullmann, Lisel Suess, Lene Hesse-Sinzheimer, Julius Suess, ?, Hermann Boehm, Eugen Hirsch, Dr. Carl Kahn, Frau von Michael Rothschild (Ella?), Max Sinzheimer, Grete Hirschland and Alfred Liebmann ; Seated l-r: Adele Boehm, Michael Rothschild, rosel Suess, Louis Kahn (Junior), Ehepaar Dr. Gustav Hecht, Paula Hirsch and Marianne Kahn
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(l-r): Ruth Altman, Irene Hirsch, Hilde Dannhauser, Suse Barth, Anneliese Hirsch, Suse Saenger, Esther Nathan, Hannelore Baer, Heinz Koerner, Ruth Bauland, Marianne Leiter, Heinz Krippel, Hanna Ullmann, Edith Weil, Otto Eckstein, Susi Ehrlich, Hans Klein, Julie Klappholz, Hanna Chose, Minna Hirsch and Rudolf Loewy
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To evaluate the interlaboratory mass bias for high-precision stable Mg isotopic analysis of natural materials, a suite of silicate standards ranging in composition from felsic to ultramafic were analyzed in five laboratories by using three types of multicollector inductively coupled plasma mass spectrometer (MC-ICPMS). Magnesium isotopic compositions from all labs are in agreement for most rocks within quoted uncertainties but are significantly (up to 0.3 parts per thousand in Mg-26/Mg-24, > 4 times of uncertainties) different for some mafic samples. The interlaboratory mass bias does not correlate with matrix element/Mg ratios, and the mechanism for producing it is uncertain but very likely arises from column chemistry. Our results suggest that standards with different matrices are needed to calibrate the efficiency of column chemistry and caution should be taken when dealing with samples with complicated matrices. Well-calibrated standards with matrix elements matching samples should be used to reduce the interlaboratory mass bias.
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Several new ligand platforms designed to support iron dinitrogen chemistry have been developed. First, we report Fe complexes of a tris(phosphino)alkyl (CPiPr3) ligand featuring an axial carbon donor intended to conceptually model the interstitial carbide atom of the nitrogenase iron-molybdenum cofactor (FeMoco). It is established that in this scaffold, the iron center binds dinitrogen trans to the Calkyl anchor in three structurally characterized oxidation states. Fe-Calkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe-Calkyl interaction. The anionic (CPiPr3)FeN2- species can be functionalized by a silyl electrophile to generate (CPiPr3)Fe-N2SiR3. This species also functions as a modest catalyst for the reduction of N2 to NH3. Next, we introduce a new binucleating ligand scaffold that supports an Fe(μ-SAr)Fe diiron subunit that coordinates dinitrogen (N2-Fe(μ-SAr)Fe-N2) across at least three oxidation states (FeIIFeII, FeIIFeI, and FeIFeI). Despite the sulfur-rich coordination environment of iron in FeMoco, synthetic examples of transition metal model complexes that bind N2 and also feature sulfur donor ligands remain scarce; these complexes thus represent an unusual series of low-valent diiron complexes featuring thiolate and dinitrogen ligands. The (N2-Fe(μ-SAr)Fe-N2) system undergoes reduction of the bound N2 to produce NH3 (~50% yield) and can efficiently catalyze the disproportionation of N2H4 to NH3 and N2. The present scaffold also supports dinitrogen binding concomitant with hydride as a co-ligand. Next, inspired by the importance of secondary-sphere interactions in many metalloenzymes, we present complexes of iron in two new ligand scaffolds ([SiPNMe3] and [SiPiPr2PNMe]) that incorporate hydrogen-bond acceptors (tertiary amines) which engage in interactions with nitrogenous substrates bound to the iron center (NH3 and N2H4). Cation binding is also facilitated in anionic Fe(0)-N2 complexes. While Fe-N2 complexes of a related ligand ([SiPiPr3]) lacking hydrogen-bond acceptors produce a substantial amount of ammonia when treated with acid and reductant, the presence of the pendant amines instead facilitates the formation of metal hydride species.
Additionally, we present the development and mechanistic study of copper-mediated and copper-catalyzed photoinduced C-N bond forming reactions. Irradiation of a copper-amido complex, ((m-tol)3P)2Cu(carbazolide), in the presence of aryl halides furnishes N-phenylcarbazole under mild conditions. The mechanism likely proceeds via single-electron transfer from an excited state of the copper complex to the aryl halide, generating an aryl radical. An array of experimental data are consistent with a radical intermediate, including a cyclization/stereochemical investigation and a reactivity study, providing the first substantial experimental support for the viability of a radical pathway for Ullmann C-N bond formation. The copper complex can also be used as a precatalyst for Ullmann C-N couplings. We also disclose further study of catalytic Calkyl-N couplings using a CuI precatalyst, and discuss the likely role of [Cu(carbazolide)2]- and [Cu(carbazolide)3]- species as intermediates in these reactions.
Finally, we report a series of four-coordinate, pseudotetrahedral P3FeII-X complexes supported by tris(phosphine)borate ([PhBP3FeR]-) and phosphiniminato X-type ligands (-N=PR'3) that in combination tune the spin-crossover behavior of the system. Low-coordinate transition metal complexes such as these that undergo reversible spin-crossover remain rare, and the spin equilibria of these systems have been studied in detail by a suite of spectroscopic techniques.
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A highly efficient Cu-catalyzed C-O bond-forming reaction of alcohol and aryl bromides has been developed. This transformation was realized through the use of copper(I) iodide as a catalyst, 8-hydroxyquinoline as a ligand, and K3PO4 as a base. A variety of functionalized substrates were found to react under these reaction conditions to provide products in good to excellent yields.
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Monodisperse carbazole-based oligomers have been synthesized via C-N bonds formation by the modified Ullmann reaction. The full characterization of their structure is presented. These derivatives are highly thermally stable amorphous compounds with glass transition temperatures of 167-171 degrees C and thermal decomposition temperatures of ca. 400 degrees C. Amorphous films of the materials were fabricated and their hole-transporting properties were tested in a light emitting device with Alq(3) as an electroluminescent and electron-transporting material.
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Two kinds of carbazole-based molecules connected with diphenylamine and carbazole are synthesized by modified Ullmann reaction. Comparative study on their thermal stability, redox behavior, hole injection and transport properties are present. The results demonstrate that the carbazole-based molecules are very promising hole-transporting materials for electroluminescent devices.
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The basic definition of a cabaret is a café that offers live entertainment performed by singers, musicians and dancers and serves food and drink. It is generally housed in small, intimate spaces. Starting in the middle of the nineteenth century, artists, composers and writers met at Parisian cafés and salons to share their works. The cabaret was a suitable place for social activities. Artists could meet, discuss their opinions, and share their art in a relaxed setting. Even though cabaret music was often based on popular idioms, social and political commentary coupled with satirical settings represented the true soul of the genre. This trend flourished in the late nineteenth and early twentieth centuries. The first cabaret in Paris, Le Chat Noir inspired the growth of similar places in major cities throughout Europe besides Paris. The three recitals that comprise this dissertation project were performed at University of Maryland venues: the Robert & Arlene Kogod Theatre on 11 May 2011, Ulrich Recital Hall on 4 December 2011, and Gildenhorn Recital Hall on 4 March 2012. The repertoire for the first recital included works by Erik Satie with mezzo-soprano Monica Soto-Gil, Friedrich Hollaender with soprano Gabrielle DeMers, William Bolcom with baritone Ethan Watermeier and mezzo-soprano Stepanie Sadownik, and Poulenc with baritone Andrew McLaughlin. André Previn‘s Tango Song and Dance with violinist Jennifer Kim served as the instrumental interlude. The second recital included songs by Friedrich Hollaender with mezzo-soprano Monica Soto-Gil, Hanns Eisler and Viktor Ullmann with mezzo-soprano Stephanie Sadownik, and Mischa Spoliansky with soprano CarrieAnne Winter. Victor Hollaender‘s Romance and Albumblatt were the instrumental interludes with violinist Jennifer Kim. The last recital featured works for piano and violin, the Graceful Ghost Rag by William Bolcom with violinist Jenny Wu, Four Souvenirs by Paul Schoenfield with violinist Jennifer Kim, Cabaret Songs by Benjamin Britten with soprano Linda Mabbs, and Souvenirs for piano four-hands by Samuel Barber with pianist Rita Sloan. The recitals were recorded on compact discs and are archived within the Digital Repository at the University of Maryland (DRUM).
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Were study a horse (Equus caballus), Purebred Spanish Horse, 6 years old, intact male sex, weight about 550kg, from equestrian center in Fregenal Sierra-Extremadura, Spain. History of acute diarrhea, are apply conventional treatment (hydration, anti-inflammatory and antibiotic). Physical examination showed severe profuse, fetid diarrhea deep red, tachypnea. The physiological parameters were: heart rate 60 bpm, respiratory rate 39 rpm and mucous cyanotic. Temperature: 40°C. Hematological examination showed severe leucopenia, decreased total serum protein, albumin and globulin also diminished. Serum chemistry evidenced severe hyponatremia and hypokalemia, with high levels of chlorine indicating metabolic acidosis. A stool analysis, which was negative and showed no eggs or larvae in the samples studied was performed. The microbial culture allowed the isolation of Klebsiella sp. and susceptibility testing showed sensitivity to ampicillin, Cetafzidine, Ciprofloxacin, Cefepine, gentamicin, imipenem, meropenem, Piperaciclina, piperacillin / tazobactam and trimethoprim sulfa resistance. The horse presented systemic complications associated with endotoxemia and death 36 hours after the onset of diarrhea. At necropsy, severe bleeding was observed enterotiflocolitis. The histological sections showed proliferative enteritis characterized by lymphocyte and mononuclear inflammatory infiltrate plasmocytorious mucosa and submucosa, coagulation necrosis, bacteria and short rod type morphology with no specific grouping. In conclusion a case of acute syndrome enterotiflocolitis reported Klebsiella sp. on a horse Purebred Spanish.
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A German university has developed a learning information system to improve information literacy among German students. An online tutorial based on this Lerninformationssystem has been developed. The structure of this learning information system is described, an online tutorial based on it is illustrated, and the different learning styles that it supports are indicated.
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Die Autoren beschreiben das von ihnen entwickelte Lerninformationssystem zur Informationskompetenz. Der Artikel behandelt den Aufbau und die Perspektiven des Systems.
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Zuerst wird auf die Wichtigkeit bibliotheks- und informationswissenschaftlicher Fachkommunikation eingegangen. Die Eignung von Blogs zur Kommunikation innerhalb einer wissenschaftlichen Disziplin wird hervorgehoben. Es folgt eine allgemeine Typologie der Blogger. Abschließend wird das Projekt LibWorld des Fachblogs Infobib vorgestellt. Im Rahmen dieses Projektes stellen Gastautoren aus zahlreichen Ländern die Biblioblogosphäre (bibliotheksrelevante Blogs) ihrer Heimat vor.
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On April, 23rd 2007 a series of postings started on Infobib.de, where guest authors from all over the world introduced the library and library related blogs of their own country. This book is a collection of 30 revised LibWorld articles, accompanied by a foreword by Walt Crawford. Included are articles about the blogosphere of: Argentina, Australia, Austria, Belarus, Belgium, Brazil, Canada, Denmark, Finland, France, Greece, Hungary, Iran, Italy, Japan, Latvia, Malawi, Netherlands, New Zealand, Norway, Peru, Puerto Rico, Russia, Singapore, Spain, Sweden, Switzerland, Trinidad & Tobago, USA.
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The process to develop a guideline in a European setting remains a challenge. The ESCMID Fungal Infection Study Group (EFISG) successfully achieved this endeavour. After two face-to-face meetings, numerous telephone conferences, and email correspondence, an ESCMID task force (basically composed of members of the Society's Fungal Infection Study Group, EFISG) finalized the ESCMID diagnostic and management/therapeutic guideline for Candida diseases. By appreciating various patient populations at risk for Candida diseases, four subgroups were predefined, mainly ICU patients, paediatric, HIV/AIDS and patients with malignancies including haematopoietic stem cell transplantation. Besides treatment recommendations, the ESCMID guidelines provide guidance for diagnostic procedures. For the guidelines, questions were formulated to phrase the intention of a given recommendation, for example, outcome. The recommendation was the clinical intervention, which was graded by a score of A-D for the 'Strength of a recommendation'. The 'level of evidence' received a score of I-III. The author panel was approved by ESCMID, European Organisation for Research and Treatment of Cancer, European Group for Blood and Marrow Transplantation, European Society of Intensive Care Medicine and the European Confederation of Medical Mycology. The guidelines followed the framework of GRADE and Appraisal of Guidelines, Research, and Evaluation. The drafted guideline was presented at ECCMID 2011 and points of discussion occurring during that meeting were incorporated into the manuscripts. These ESCMID guidelines for the diagnosis and management of Candida diseases provide guidance for clinicians in their daily decision-making process.